CN104947093B - The method and a kind of wiring board and its manufacturing method of a kind of chemical nickel-plating liquid and a kind of chemical nickel plating - Google Patents
The method and a kind of wiring board and its manufacturing method of a kind of chemical nickel-plating liquid and a kind of chemical nickel plating Download PDFInfo
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Abstract
The invention discloses a kind of chemical nickel-plating liquid and a kind of method of chemical nickel plating, which contains hypophosphites, nickel salt, Nano silver grain, anionic surfactant, complexing agent, buffer and stabilizer, and the pH value of chemical nickel-plating liquid is 45；The content of Nano silver grain is 1.0 × 10‑6‑1.0×10‑4Mol/L, the content of anionic surfactant is 30 70 mg/litres.The present invention also provides a kind of wiring board and its manufacturing method, the wiring board include ceramic substrate, at least one surface for being attached to the ceramic substrate copper wire layer and be attached to the nickel layer on copper wire layer surface, be dispersed with Nano silver grain in nickel layer.Chemical plating is carried out on substrate using chemical nickel-plating liquid provided by the invention, higher plating rate can under equal conditions be obtained, and the coating formed has higher adhesive force to substrate, and the conductive capability of wiring board of the invention is strong, and with higher heat-sinking capability.
Description
Technical field
The present invention relates to a kind of chemical nickel-plating liquid and a kind of method of chemical nickel plating, the invention further relates to a kind of wiring board and
Its manufacturing method.
Background technology
Chemical nickel plating, also known as electroless nickel plating or autocatalytic nickel, be by reducing agent appropriate in solution make nickel from
The nickel deposition process that son is carried out in metal surface by the reduction of self-catalysis.In assist side, pass through the copper of assist side
Nickel layer is formed between line layer and layer gold, to avoid wiring board solderability difference caused by the phase counterdiffusion between copper gold and can be used
The defects of short life, meanwhile, the nickel layer of formation also improves the mechanical strength of metal layer.
Nano material has the characteristics that small-size effect, skin effect, quantum size effect and macro quanta tunnel effect,
Nano-particle is added in chemical plating fluid, it is made to become electroless nanometer composite coating, base together with deposited metal under stirring
In the special nature of nano-particle, electroless nanometer composite coating obtained therefore has and includes corrosion resistance, wearability, high temperature resistance
The excellent performance such as oxidisability and electrocatalysis.The domestic research to electroless nanometer composite coating nickel technique at present, mainly in Ni-
Inorganic nano-particle is added in P plating solutions, such as Si, SiO2、SiC、Al2O3Deng for improving the corrosion resistance of coating, wearability, anti-height
Warm oxidisability and electrocatalysis etc..But nano-particle is easily reunited in Ni-P/ nano-particle chemistry plating solutions, and plating solution is difficult to keep
Stability.And the nickel layer that the Ni-P plating solutions containing these nano-particles are formed in the circuit board is thicker, and the resistance of nickel is much larger than
The resistance of copper wire layer on substrate, therefore the electric conductivity of wiring board certainly will be influenced.In addition, the substrate of most of wiring boards is gold
Belong to substrate, also lead to the heat-sinking capability of wiring board to reduce, although and ceramic substrate with higher heat-sinking capability, ceramic base
The binding force between copper wire layer and nickel layer on plate is generally relatively low, so as to limit wiring board in high-capacity LED, headlight for vehicles
And the application in high power component.
Invention content
It is an object of the invention to solve the bad technology of wiring board electric conductivity and heat dissipation performance of the prior art to ask
Topic, so as to provide the manufacturing method and circuit of a kind of method of chemical nickel-plating liquid and a kind of chemical nickel plating and a kind of wiring board
Plate.
The present inventor has been surprisingly found that in the course of the research：If the silver of certain content is added in chemical nickel-plating liquid
Nano-particle forms nickel layer, finally formed wiring board tool on the surface of the line layer of ceramic substrate using the chemical nickel-plating liquid
There are good electric conductivity and heat dissipation performance.The present invention is completed on this basis.
According to the first aspect of the invention, the present invention provides a kind of chemical nickel-plating liquid, which contains secondary
Phosphate, nickel salt, Nano silver grain, anionic surfactant, complexing agent, buffer and stabilizer, the chemical nickel plating
The pH value of liquid is 4-5, wherein, the content of the Nano silver grain is 1 × 10-6-1×10-4Mol/L, the anionic table
The content of face activating agent is 30-70 mg/litres；Preferably, the content of the Nano silver grain is 0.5 × 10-5-5×10-5It rubs
You/liter, the content of the anionic surfactant is 40-50 mg/litres.
According to the second aspect of the invention, the present invention provides a kind of method of chemical nickel plating, this method is included with this
The chemical nickel-plating liquid provided is provided, chemical nickel plating is carried out to substrate to form nickel layer.
According to the third aspect of the present invention, the present invention provides a kind of manufacturing method of wiring board, the method includes
Chemical nickel plating is carried out to the copper wire layer for being attached at least one surface of substrate with chemical nickel-plating liquid to form nickel layer, and optionally
In the nickel layer surface priority plating palladium layers and layer gold of formation, wherein, the chemical nickel-plating liquid is above-mentioned chemical nickel-plating liquid.
According to the fourth aspect of the present invention, the present invention provides a kind of wiring board, the wiring board include ceramic substrate,
The copper wire layer being attached at least one surface of the ceramic substrate and the nickel layer being attached on the copper wire layer surface,
Nano silver grain is dispersed in the nickel layer, the ceramic substrate is preferably aluminum nitride ceramic substrate.
Chemical plating is carried out on substrate using chemical nickel-plating liquid provided by the invention, can under equal conditions obtain higher
Plating rate, and formed coating to substrate have higher adhesive force.
Conductive capability using the wiring board of method provided by the invention manufacture is strong, and has higher heat-sinking capability,
Therefore it can be applied in high-capacity LED, headlight for vehicles and high power component.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
According to the first aspect of the invention, the present invention provides a kind of chemical nickel-plating liquid, the chemical nickel-plating liquid contains
Hypophosphites, nickel salt, Nano silver grain, anionic surfactant, complexing agent, buffer and stabilizer, the chemical plating
The pH value of nickel liquid is 4-5, wherein, the content of the Nano silver grain is 1 × 10-6-1×10-4Mol/L, the anionic
The content of surfactant is 30-70 mg/litres.
According to the present invention, in the chemical nickel-plating liquid content of Nano silver grain can according to expected nickel layer thickness and
Expected resistivity is selected.In the present invention, the content of the Nano silver grain is 1 × 10-6-1×10-4Mol/L.
When the content of the Nano silver grain is within above range, it can not only cause the nickel layer to be formed that there is relatively low resistance
Rate, so that finally formed wiring board has higher electric conductivity；And the nickel layer formed also have it is higher wear-resisting
Damage performance.Preferably, the content of the Nano silver grain is 0.5 × 10-5-5×10-5Mol/L.
The granular size of the Nano silver grain, which is subject to, can form fine and close nickel layer.Preferably, the nano grain of silver
The volume average particle size D of son50For 10-50nm, fine and close nickel layer can be formed in this way.It is highly preferred that the Nano silver grain
Volume average particle size D50For 15-30nm.In the volume average particle size D of the Nano silver grain50During for 15-30nm, the silver is received
Rice corpuscles has larger specific surface area, is on the one hand more easily dispersed in the chemical nickel-plating liquid, on the other hand causing
State when chemical nickel-plating liquid forms certain thickness nickel layer can the Nano silver grain containing high level, so as to reduce the nickel layer
Resistivity.The volume average particle size D of the Nano silver grain50It can be measured according to Malvern laser particle size analyzer.
The Nano silver grain can be obtained according to the method for this field routine.It for example, can be according to CN1803350A's
Method prepares the different Nano silver grain of average grain diameter.In addition, the Nano silver grain can be commercially available, for example,
Purchased from Beijing Deco Dao Jin Science and Technology Ltd.s, the trade mark is the product of DK101 or DK101-1.
According to the present invention, the anionic surfactant can promote the effusion of gas in chemical nickel-plating liquid, and drop
The porosity of coating that the low chemical nickel-plating liquid is formed.The dosage of surfactant is can realize in the chemical nickel-plating liquid
Subject to above-mentioned function.In the present invention, the content of the anionic surfactant is 30-70 mg/litres, can be formed in this way
More fine and close nickel layer.Preferably, the content of the anionic surfactant is 40-50 mg/litres.
The present inventor has found in the course of the research, in the chemical nickel-plating liquid, when the content of the Nano silver grain
It is 0.5 × 10-5-5×10-5Mol/L, when the content of the anionic surfactant is 40-50 mg/litres, formation
Silver nanoparticle dispersion is more uniformly distributed in nickel layer, is avoided due to a certain position in Nano silver grain concentration assist side and conducting wire
The problem of road plate destroys.
The anionic surfactant can be common anionic surfactant.Preferably, it is described it is cloudy from
Subtype surfactant is dodecyl sodium sulfate, lauryl sodium sulfate, sulfosuccinic acid monoesters disodium and fatty acid methyl ester
Ethoxylate sulfonates（FMES）One or more of.
The structure such as formula of the sulfosuccinic acid monoesters disodium（1）It is shown：
Wherein, R can be the saturated or unsaturated alkyl of C12-C18, and the alkyl can be the hydrocarbon of linear chain or branch chain
Base；N can be arbitrary integer in 0-10.
The sulfosuccinic acid monoesters disodium can be commercially available, for example, limited purchased from Shanghai Jinshan longitude and latitude chemical industry
The trade mark of company is the product of mes.
The fatty acid methyl ester ethoxylate sulfonate can be commercially available, for example, purchased from happiness He Shihua.
In the preferred embodiment of the present invention, the anionic surfactant for dodecyl sodium sulfate and
And lauryl sodium sulfate, and dodecyl sodium sulfate and the mass ratio of lauryl sodium sulfate are 1: 1-3, are enabled in this way
Finally formed wiring board has better electric conductivity.
According to the present invention, in the chemical nickel-plating liquid, the content of the hypophosphites and the nickel salt can be ability
The customary amount in domain.For example, the content of the hypophosphites can be 15-50 g/l, the content of the nickel salt can be 12-
45 g/l.Under preferable case, the content of the hypophosphites is 20-45 g/l, and the content of the nickel salt is 20-35 g/l,
It can make the chemical nickel-plating liquid that there is higher stability in this way, and enable the chemical nickel-plating liquid more when forming nickel layer
Capture the Nano silver grain in ground.
The present invention is not particularly limited the type of the nickel salt and hypophosphites, can be conventional selection.
Specifically, the nickel salt can be one or more of nickel sulfate, nickel chloride and nickel acetate, preferably sulphur
Sour nickel.
The hypophosphites can be sodium hypophosphite and/or potassium hypophosphite.From the angle for reducing the chemical nickel-plating liquid cost
Degree sets out, and the hypophosphites is preferably sodium hypophosphite.
According to the present invention, the chemical nickel-plating liquid can also contain stabilizer, buffer and complexing agent, to avoid chemical plating
The decomposition of nickel liquid and precipitation.The present invention is not particularly limited the type and its content of the stabilizer and complexing agent.
The stabilizer can be at least one of sodium thiosulfate, potassium thiosulfate, thiocarbamide and xanthate.It is preferred that
Ground, the stabilizer are thiocarbamide.The content of the stabilizer can be 0.5-5 mg/litres.
The buffer can be at least one of sodium acetate, sodium succinate and natrium hydrocitricum.Preferably, it is described slow
Electuary is sodium acetate.The content of the buffer can be 5-20 g/l.
The complexing agent can be in succinic acid, sodium succinate, citric acid, sodium citrate, lactic acid, malic acid and glycine
At least one, preferably sodium citrate.The content of the complexing agent can be 20-40 g/l.
According to the present invention, in order to meet the requirement of chemical plating process, the pH of the chemical nickel-plating liquid is 4-5.
According to the present invention, the chemical nickel-plating liquid can be by that will contain the Nano silver grain and the anionic table
After the aqueous solution of face activating agent is mixed with the aqueous solution containing nickel salt, hypophosphites, stabilizer, buffer and complexing agent, so as to
Chemical nickel-plating liquid is made.In following embodiment and comparative example, use hydrochloric acid or sodium carbonate adjust the pH of the chemical nickel-plating liquid for
4-5。
Aqueous solution containing Nano silver grain and anionic surfactant can pass through the condition in supersonic oscillations
Under, Nano silver grain and anionic surfactant are dispersed in water and obtained.
According to the second aspect of the invention, the present invention provides a kind of method of chemical nickel plating, this method includes useization
It learns nickel-plating liquid and chemical nickel plating is carried out to substrate to form nickel layer, the chemical nickel-plating liquid is above-mentioned chemical nickel-plating liquid.
In the present invention, activated substrate can be placed in chemical plating provided by the invention under the conditions of chemical nickel plating
In nickel liquid, so as to form nickel layer in substrate surface.Specifically, it is 75-90 DEG C that substrate can be placed in temperature（Such as 80-85 DEG C）'s
In the chemical nickel-plating liquid of the present invention, so as to form nickel layer in substrate surface.The time of the chemical nickel plating can be according to substrate
The thickness of type and expected nickel layer is selected, and generally can be 20-70 minutes.
The substrate can be the substrate of a variety of materials, for example, can be resin substrate, ceramic substrate or metal substrate.
According to the third aspect of the present invention, the present invention provides a kind of manufacturing method of wiring board, this method includes using
Chemical nickel-plating liquid carries out chemical nickel plating to form nickel layer and optionally exist to the copper wire layer for being attached at least one surface of substrate
The nickel layer surface priority plating palladium layers and layer gold of formation, wherein, the chemical nickel-plating liquid is chemical nickel-plating liquid provided by the invention.
From the angle for improving the wiring board heat-sinking capability, the substrate of the wiring board is preferably ceramic substrate, institute
It can be aluminium oxide ceramic substrate, aluminum nitride ceramic substrate or silicon nitride ceramic substrate to state ceramic substrate.It is highly preferred that the pottery
Porcelain substrate is aluminum nitride ceramic substrate, can obtain the better wiring board of heat dissipation performance in this way, and nickel layer is on substrate surface
Copper wire layer adhesive force higher.
Copper wire layer on substrate of the present invention can be made according to the method for this field routine.Usually, in the substrate
During for ceramic substrate, thick film technology may be used, i.e., copper slurry is coated on substrate surface using print process, then through heat at
Reason, metal pulp are sintered and obtain layers of copper；It is or using thin film technique, i.e., right by the film molding of the vacuum such as sputtering, vacuum evaporation
Ceramic base plate surface metallizes, and the copper wire layer is formed through photoetching, etching work procedure.The tool that the copper wire layer is formed
Body step is the selection of this field routine, and details are not described herein.
It in the present invention, can be by using chemical nickel-plating liquid provided by the invention to being attached at least one table of substrate
The copper wire layer in face carries out chemical nickel plating to form the nickel layer of the wiring board.Usually, at least one surface can be included
It is 80-90 DEG C that the substrate of copper wire layer, which is placed in temperature,（Such as 83-86 DEG C）The present invention chemical nickel-plating liquid in, so as in copper wire
The surface of layer forms nickel layer.The time of the chemical nickel plating can be selected according to the thickness of expected nickel layer, generally can be with
It is 20-40 minutes.
According to the present invention, the condition of the chemical nickel plating is preferably so that the thickness of the nickel layer formed in copper wire layer is 3-
7 μm, it can make wiring board obtained that there is higher electric conductivity and heat dissipation performance and reduce the time of reaction in this way.Institute
Stating the thickness of nickel layer can measure according to x ray fluorescence spectrometry.
Chemistry is carried out in the chemical nickel-plating liquid for being placed in the present invention in the substrate that at least one surface is attached with to copper wire layer
Before nickel plating, method commonly used in the art may be used, the surface of copper wire layer is activated.The present invention for will need into
The method that the surface of the copper wire layer of row chemical nickel plating is activated is not particularly limited, and the conventional method of this field may be used
It carries out.
Usually, substrate can be put into the aqueous solution containing palladium activator and acid, will needs to form the copper of coating
Line layer activates.The palladium activator can be palladium bichloride or palladium sulfate, preferably palladium bichloride, and the acid is preferably a concentration of 37
The hydrochloric acid of weight %.The content of the palladium activator and acid can be conventional selection.Usually, the content of the palladium activator can
Think 0.2-2.5g/L, the content of the hydrochloric acid of a concentration of 37 weight % can be 180-250mL/L.Contain palladium activator and acid
The pH value of aqueous solution generally can be 3-5.
When being activated, the temperature of the aqueous solution containing palladium activator and acid can be 25-35 DEG C.Palladium activation when
Between generally can be 30-90 seconds.
According to the present invention, after forming nickel layer on the surface of the copper wire layer, the method can also be included in what is formed
The method of nickel layer surface priority plating palladium layers and layer gold, plating palladium layers and layer gold is the method for this field routine.
Specifically, the substrate that chemical nickel plating obtains can be placed in chemical palladium plating solution and carries out chemical palladium-plating, with described
Palladium layers are formed on the surface of nickel layer.The chemical palladium plating solution can contain palladium salt, reducing agent, complexing agent and stabilizer.The palladium
Salt can be one or more of palladium bichloride, palladium bromide and palladium sulfate, the reducing agent can be sodium hypophosphite, hydrazine or
Dimethylamine borane, the complexing agent can be ethylenediamine tetra-acetic acid and/or ethylenediamine, and the stabilizer can be ammonium chloride, sulphur
One or more of sodium thiosulfate and thioglycol acid.
In the chemical palladium plating solution, the content of the palladium salt can be 3-10g/L, and the content of the reducing agent can be
0.5-15g/L, the content of the complexing agent can be 15-35g/L, and the content of the stabilizer can be 15-30mg/L.
The condition of the chemical palladium-plating can include：PH value is 7-8, and temperature is 40-60 DEG C（Such as 45-55 DEG C）.Describedization
The processing time for learning plating palladium can be 7-12min, preferably 8-10min.
The substrate that chemical palladium-plating obtains can be placed in chemical gold plating liquid, to be further formed layer gold on palladium layers surface.
The chemical gold plating liquid can contain gold salt, reducing agent and complexing agent.The gold salt can be potassium auricyanide, gold potassium cyanide and
One or more of gold chloride, the reducing agent can be sodium hypophosphite, potassium borohydride, hydrazine or dimethylamine borane, institute
It can be at least one of potassium cyanide, ethylenediamine tetra-acetic acid and ethanol amine to state complexing agent.
In the chemical gold plating liquid, the content of the gold salt can be 2-7g/L, and the content of the reducing agent can be 4-
12g/L, the content of the complexing agent can be 3-8g/L.
The condition of the chemical gilding can include：PH value is 11-13, and temperature is 80-85 DEG C.The place of the chemical gilding
It can be 8-11min to manage the time.
In addition, before the surface to the copper wire layer activates, method commonly used in the art may be used to copper
Line layer carries out degreasing, and carries out microetch to the copper wire layer after degreasing.The method of the degreasing can be the routine of this field
Selection, is no longer described in detail herein.
The method of the microetch can include：Microetch is carried out to the copper wire layer with micro-etching agent.Preferably, the microetch
Contain sulfuric acid, hydrogen peroxide, copper chloride and stabilizer in agent.The content of the sulfuric acid can be 45-90g/L, hydrogen peroxide
Content is 9-25g/L, and the content of copper chloride is 15-35g/L, and the content of the stabilizer is 0.2-1.5g/L, can be made in this way
There is higher adhesive force between the nickel layer and copper wire layer that are formed after obtaining through the chemical nickel plating.
In the micro-etching agent, stabilizer is preferably benzotriazole and/or salicylic acid.
According to the present invention, in order to improve the rate of the microetch, the pH value of the micro-etching agent can be 2-4.
When carrying out microetch, the temperature of the microetch can be 15-35 DEG C；The time of the microetch can be 20-40s.
After each step chemical plating is carried out, conventional method may be used, the substrate through chemical plating is washed.Specifically,
It can treated that substrate is put into the three-level rinsing bowl of lasting overflow handles 50-70s by each step.
After chemical plating completion, it can also include the wiring board of preparation being dried.The condition of the drying can be with
For conventional selection.For example, can first dry up the moisture of PCB surface, it is then placed in 80-100 DEG C of baking oven and dries.
According to the fourth aspect of the present invention, the present invention provides a kind of wiring board, the wiring board include ceramic substrate,
It is attached to the copper wire layer at least one surface of the ceramic substrate and the nickel layer being attached on the copper wire layer surface, institute
It states and Nano silver grain is dispersed in nickel layer.
According to the present invention, the thickness of the nickel layer resistivity and wearability can be selected according to expected from wiring board.
Preferably, the thickness of the nickel layer is 3-7 μm.
The content of the Nano silver grain can be selected according to the resistivity of nickel layer.Preferably, the nano grain of silver
The content of son so that the resistivity of the nickel layer is 4-15 μ Ω cm-1。
Wiring board according to the present invention, the ceramic substrate can be aluminium oxide ceramic substrate, aluminum nitride ceramic substrate or
Silicon nitride ceramic substrate.Preferably, the ceramic substrate is aluminum nitride ceramic substrate
To the present invention be more fully described by embodiment below.
In following embodiment and comparative example, acid degreasing agent is purchased from Shenzhen Success Technology Co., Ltd., trade mark CG-
1551；The ingredient and its content of chemical palladium plating solution and chemical gold plating liquid are as shown in Table 1.
The test of nickel plating rate：The ratio of nickel layer thickness and time, that is, nickel plating rate, wherein, nickel layer thickness uses X ray
Fluorescent spectrometry measures.
The thermal conductivity test of wiring board：Using laser Conduction Coefficient Detector Basing（Originate from German Nai Chi companies, LFA447 types）, survey
It is 25 DEG C to try temperature.
The resistivity measurement of wiring board：Using four probe resistance rate sheet resistance tester of metal（It is new that energy sunlight is closed purchased from Beijing
Enertech Co., Ltd., model HS-MPRT-5）, test temperature is 25 DEG C, humidity 50%RH.
Coating adhesion is tested：Chemical Ni-plating layer sample on ceramic substrate is cut into each 5 pieces of 3mm squares in length and breadth
（Chessboard trellis）, 25 fritter, then with tape-stripping, then stripping tape, is recorded in the small block number that interior energy three times peels off altogether
N is measured, is expressed as n/25.
The hardness test of wiring board：By the method that ASTM B578-80 are provided using Japan's manufacture AKASHI microhardnesses
Meter, load 200g, each 5 points of test piece are averaged.Wiring board is heat-treated 1 hour at 400 DEG C before test.
Table 1
Embodiment 1-3
Embodiment 1-3 is used to illustrate chemical nickel-plating liquid provided by the invention and preparation method thereof.
By Nano silver grain（D50=20nm, purchased from Beijing Deco Dao Jin Science and Technology Ltd.s, trade mark DK101-1）It adds in
To dissolved with surfactant sodium dodecyl base sodium sulfonate and lauryl sodium sulfate（In embodiment 1-3, dodecyl sodium sulfate and
The mass ratio of lauryl sodium sulfate is respectively 1: 1,1: 2 and 1: 3）Aqueous solution in, in 25 DEG C of ultrasonic disperse 1h, contained
The mixed liquor of Nano silver grain.
Mixed liquor is added to the basic nickel-phosphor containing nickel sulfate, sodium hypophosphite, sodium citrate, sodium acetate and thiocarbamide to plate
In liquid, in 85 DEG C with 600 revs/min of stirring 30min, so as to which the chemical nickel-plating liquid that pH is 5 be made.Each ingredient of chemical nickel-plating liquid
Concrete content is as shown in table 2.
Embodiment 4
The present embodiment is used to illustrate chemical nickel-plating liquid provided by the invention and preparation method thereof.
Chemical nickel-plating liquid is prepared using method same as Example 1, the difference is that Nano silver grain D50=10nm（Root
It is made according to the method for embodiment in CN1803350A 1）, so as to which chemical nickel-plating liquid be made.
Embodiment 5
The present embodiment is used to illustrate chemical nickel-plating liquid provided by the invention and preparation method thereof.
Chemical nickel-plating liquid is prepared using method same as Example 1, the difference is that Nano silver grain D50=50nm（Purchase
From Beijing Deco Dao Jin Science and Technology Ltd.s, trade mark DK101）, so as to which chemical nickel-plating liquid be made.
Embodiment 6
The present embodiment is used to illustrate chemical nickel-plating liquid provided by the invention and preparation method thereof.
By Nano silver grain（D50=20nm, purchased from Beijing Deco Dao Jin Science and Technology Ltd.s, trade mark DK101-1）It adds in
To dissolved with surfactant sodium dodecyl base sodium sulfonate and lauryl sodium sulfate（Dodecyl sodium sulfate and dodecyl sulphate
The mass ratio of sodium is 1: 5）Aqueous solution in, in 25 DEG C of ultrasonic disperse 1h, obtain the mixed liquor containing Nano silver grain；
Mixed liquor is added to the basic nickel-phosphor containing nickel sulfate, sodium hypophosphite, sodium citrate, sodium acetate and thiocarbamide to plate
In liquid, in 80 DEG C with 600 revs/min of stirring 30min, so as to which the chemical nickel-plating liquid that pH is 5 be made.Each ingredient of chemical nickel-plating liquid
Concrete content is as shown in table 2.
Embodiment 7
The present embodiment is used to illustrate chemical nickel-plating liquid provided by the invention and preparation method thereof.
Chemical nickel-plating liquid is prepared using method same as Example 1, the difference is that the sulfosuccinic with equal mass
Acid monoester disodium（Purchased from Shanghai Jinshan longitude and latitude Chemical Co., Ltd., trade mark mes）Instead of the surfactant of embodiment 1, from
And chemical nickel-plating liquid is made.
Embodiment 8
The embodiment is used to illustrate chemical nickel-plating liquid provided by the invention and preparation method thereof.
Chemical nickel-plating liquid is prepared according to method described in embodiment 1, the difference is that the fatty acid methyl esters second with equal mass
Oxygroup compound sodium sulfonate（Purchased from happiness He Shihua）Instead of the surfactant of embodiment 1, so as to which chemical nickel-plating liquid be made.
Embodiment 9
The embodiment is used to illustrate chemical nickel-plating liquid provided by the invention and preparation method thereof.
Chemical nickel-plating liquid is prepared according to method described in embodiment 1, the difference is that the dodecyl sulphur with equal mass
Sour sodium replaces the surfactant of embodiment 1, so as to which chemical nickel-plating liquid be made.
Comparative example 1
Chemical nickel-plating liquid is prepared according to method described in embodiment 1, the difference is that without using Nano silver grain and surface
Activating agent, so as to which chemical nickel-plating liquid be made.
Comparative example 2
Chemical nickel-plating liquid is prepared according to method described in embodiment 1, the difference is that the dosage of Nano silver grain causes silver
The content of nano-particle is 2.0 × 10-4Mol/L, the dosage of surfactant so that the content of surfactant is 100 millis
G/l, so as to which chemical nickel-plating liquid be made.
Comparative example 3
Chemical nickel-plating liquid is prepared according to method described in embodiment 1, the difference is that the triethanolamine generation with equal mass
For the lauryl sodium sulfate in embodiment 1, so as to which chemical nickel-plating liquid be made.
Table 2
*：The amount of triethanolamine
Application Example 1
The Application Example is used to illustrate wiring board provided by the invention and preparation method thereof.
Step 1：One surface is attached with copper wire layer（Thickness is 50 μm）Aluminum nitride ceramic substrate（76mm×
12.5mm×0.5mm）It is put into the acid degreasing agent of 100mL/L and carries out degreasing, with 45 DEG C of Temperature Treatment 6min.
Step 2：Substrate after degreasing is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 50s, with thoroughly clear
Wash the remaining preceding processing procedure liquid medicine of substrate surface.
Step 3：Substrate is put into the sulfuric acid equipped with 35mL/L（98 weight % of concentration）, 20g/L hydrogen peroxide, 30g/L chlorine
Changing in the salicylic mixed solution of copper and 0.7g/L and carry out microetch, the pH for controlling mixed solution is 2-3, and 20s is handled with room temperature,
The copper oxide that copper surface oxidation is formed is removed, to obtain fresh copper circuit surface.
Step 4：Substrate after microetch is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 60s, with thoroughly clear
The remaining preceding processing procedure liquid medicine in board-washing face.
Step 5：Substrate is put into the hydrochloric acid solution of 120mL/L（A concentration of 37 weight %）Middle carry out acidification, during processing
Between for 40s, activate the substrate surface after microetch.
Step 6：Substrate after activation microetch is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 60s, with thorough
The remaining preceding processing procedure liquid medicine of plate face is cleaned at bottom.
Step 7：Substrate is put into the hydrochloric acid of palladium bichloride and 180mL/L equipped with 2g/L（A concentration of 37 weight %）It mixes molten
In liquid, the pH for controlling mixed solution is 4-5,40s is handled at a temperature of 30 DEG C, to cause the deposition of nickel metal.
Step 8：Substrate is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 60s, with thorough cleaning base plate line
Remaining preceding processing procedure liquid medicine between the floor of road.
Step 9：Substrate is put into the chemical nickel-plating liquid obtained by embodiment 1, the pH for controlling chemical nickel-plating liquid is 4-5,
20min is handled at a temperature of 85 DEG C, so as in the copper wire layer surface deposited nickel layer of substrate.
Step 10：The substrate that deposited nickel layer is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 60s, with thorough
The remaining preceding processing procedure liquid medicine of plate face is cleaned at bottom.
Step 11：Substrate is put into chemical palladium plating solution, control chemical palladium plating solution pH is 7-8, at a temperature of 48 DEG C
10min is managed, in nickel layer surface depositing palladium layer.
Step 12：The substrate that deposited palladium layers is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 60s, with thorough
The remaining preceding processing procedure liquid medicine of plate face is cleaned at bottom.
Step 13：Substrate is put into chemical gold plating liquid, the pH for controlling chemical gold plating liquid is 11-12, in 85 DEG C of temperature
Lower processing 10min, in palladium layers surface deposition thereof.
Step 14：The substrate that deposited layer gold is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 60s, with thorough
The remaining preceding processing procedure liquid medicine of plate face is cleaned at bottom.
Step 15：Substrate is put into 80 DEG C of baking oven and dries 12min, removes the moisture on substrate.
So as to which the wiring board of Application Example 1 be made, the performance of the wiring board is as shown in table 3.
Application Example 2-10
The Application Example is used to illustrate wiring board provided by the invention and preparation method thereof.
Step 1- steps 8：It is identical with the step 1- steps 8 of Application Example 1 respectively.
Step 9：Substrate is respectively put into chemical nickel-plating liquid made from embodiment 1-9, the pH for controlling chemical nickel-plating liquid is
4-5 handles 25min at a temperature of 85 DEG C, so as in the copper wire layer surface deposited nickel layer of substrate.
Step 10：Substrate is sequentially placed into the three-level rinsing bowl of lasting overflow and handles 60s, it is residual thoroughly to clean plate face
The preceding processing procedure liquid medicine stayed.
Step 11：Substrate is put into 80 DEG C of baking oven and dries 12min, removes the moisture on substrate.
So as to which the wiring board of Application Example 2-10 be made, the performance of wiring board is as shown in table 3.
Application Example 11
Wiring board is prepared using the method identical with Application Example 2, the difference is that in step 3, substrate is put into and is matched
There is the sulfuric acid of 25mL/L（Strength by weight 98%）, the hydrogen peroxide of 30g/L, 30g/L copper chlorides and 1.7g/L salicylic mixing
Microetch is carried out in solution, the pH for controlling mixed solution is 2-3, and 20s is handled with room temperature, removes the oxidation that copper surface oxidation is formed
Copper, to obtain fresh copper circuit surface, so as to which wiring board be made.The performance of wiring board is as shown in table 3.
Comparison study example 1-3
Wiring board is prepared using the method identical with Application Example 2, the difference is that comparative example 1-3 systems are respectively adopted
The chemical nickel liquid obtained carries out chemical nickel plating to the copper wire layer on substrate, so as to which wiring board be made.The performance of wiring board such as 3 institute of table
Show.
Table 3
*：The thickness of palladium layers is 0.12 μm, and the thickness of layer gold is 0.08 μm.
From table 3 it can be seen that there is higher adhesive force between the nickel layer and copper wire layer of the wiring board of the present invention.This hair
Bright wiring board not only has higher hardness, and then with preferable abrasion resistance properties；Also have higher electric conductivity and
The capacity of heat transmission, so as to be applied in high-capacity LED, headlight for vehicles and high power component.
The foregoing describe the preferred embodiment of the present invention, still, the tool during present invention is not limited to the embodiments described above
Body details within the scope of the technical concept of the present invention, can carry out a variety of simple variants, these letters to technical scheme of the present invention
Monotropic type all belongs to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (8)
1. a kind of chemical nickel-plating liquid, the chemical nickel-plating liquid contains hypophosphites, nickel salt, Nano silver grain, anionic surface
Activating agent, complexing agent, buffer and stabilizer, the pH value of the chemical nickel-plating liquid is 4-5, wherein, in the chemical nickel-plating liquid,
The content of the hypophosphites is 15-50 g/l, and the content of the nickel salt is 12-45 g/l, and the content of the complexing agent is
20-40 g/l, the content of the buffer is 5-20 g/l, and the content of the stabilizer is 0.5-5 mg/litres, the silver
The content of nano-particle is 1 × 10-6-1×10-4Mol/L, the content of the anionic surfactant is 30-70 millis
G/l；The anionic surfactant is dodecyl sodium sulfate and lauryl sodium sulfate, and dodecyl sodium sulfate
Mass ratio with lauryl sodium sulfate is 1：1-3.
2. chemical nickel-plating liquid according to claim 1, wherein, the content of the Nano silver grain is 0.5 × 10-5-5×
10-5Mol/L, the content of the anionic surfactant is 40-50 mg/litres.
3. chemical nickel-plating liquid according to claim 1, wherein, the volume average particle size D of the Nano silver grain50For 10-
50nm。
4. a kind of method of chemical nickel plating, this method includes carrying out chemical nickel plating to substrate to form nickel layer with chemical nickel-plating liquid,
The chemical nickel-plating liquid is the chemical nickel-plating liquid described in any one in claim 1-3.
5. a kind of manufacturing method of wiring board, the method includes with chemical nickel-plating liquid to being attached at least one surface of substrate
Copper wire layer carry out chemical nickel plating to form nickel layer, and optionally in the nickel layer surface priority plating palladium layers and layer gold of formation,
In, the chemical nickel-plating liquid is the chemical nickel-plating liquid described in any one in claim 1-3.
6. according to the method described in claim 5, wherein, the substrate is ceramic substrate.
7. according to the method described in claim 6, wherein, the substrate is aluminum nitride ceramic substrate.
8. according to the method described in claim 5, wherein, with chemical nickel-plating liquid to being attached to the copper at least one surface of substrate
Before line layer carries out chemical nickel plating, the method is further included carries out the copper wire layer microetch, the microetch with micro-etching agent
Containing sulfuric acid, hydrogen peroxide, copper chloride and stabilizer in agent, and the content of sulfuric acid is 45-90g/L, and the content of hydrogen peroxide is
9-25g/L, the content of copper chloride is 15-35g/L, and the content of the stabilizer is 0.2-1.5g/L；The pH value of the micro-etching agent
For 2-4.
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| CN108336370B (en) * | 2018-02-02 | 2020-05-05 | 浙江金康铜业有限公司 | Multidimensional structure copper alloy electrode |
| CN111014722B (en) * | 2020-03-06 | 2022-05-10 | 湖南有色金属职业技术学院 | Method for preparing silver nanoclusters with strong fluorescence emission in soda ash environment |
| CN114765923A (en) * | 2021-05-20 | 2022-07-19 | 上海贺鸿电子科技股份有限公司 | Three-layer circuit board of 5G base station isolator and preparation method thereof |
| CN116770282B (en) * | 2023-07-04 | 2024-03-19 | 江苏贺鸿电子有限公司 | Chemical nickel plating process for circuit board |
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